Mn K-edge X-ray absorption spectroscopy experiments were performed on the solid- and solution-phase samples of [MnII(dpaqR)](OTf) (R=H, Me) and [MnIII(OH)(dpaqR)](OTf). The extended X-ray absorption fine structure (EXAFS) data show distinct differences between the MnII and MnIII-OH complexes, with fits providing metric parameters in excellent agreement with values from X-ray crystallography and density functional theory (DFT) computations. Evaluation of the EXAFS data for solid-phase [MnIII(OH)(dpaq)](OTf) resolved a short Mn-OH bond distance of 1.79Å; however, the short trans-amide nitrogen bond of the supporting ligand precluded the resolution of the Mn-OH bond distance in the corresponding solution-phase sample and for both [MnIII(OH)(dpaqMe)](OTf) samples. The edge energy also increases by approximately 2eV from the MnII to the MnIII-OH complexes. Experimental pre-edge analysis shows the MnII complexes to have pre-edge areas comparable to the MnIII-OH complexes, despite the presence of the relatively short Mn-OH distance. Time-dependent density functional theory (TD-DFT) computations illustrate that Mn 3d-4p mixing, a primary contributor to pre-edge intensities, decreases by~0.3% from the MnII to MnIII-OH complexes, which accounts for the very similar pre-edge areas. Collectively, this work shows that combined EXAFS and XANES analysis has great potential for identification of reactive MnIII-OH intermediates, such as those proposed in enzyme active sites.